CN113363628B - Electrolyte for aluminum-air battery and preparation method thereof - Google Patents
Electrolyte for aluminum-air battery and preparation method thereof Download PDFInfo
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- CN113363628B CN113363628B CN202110620014.3A CN202110620014A CN113363628B CN 113363628 B CN113363628 B CN 113363628B CN 202110620014 A CN202110620014 A CN 202110620014A CN 113363628 B CN113363628 B CN 113363628B
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- organic framework
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002562 thickening agent Substances 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 23
- 239000012670 alkaline solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000230 xanthan gum Substances 0.000 claims description 14
- 229920001285 xanthan gum Polymers 0.000 claims description 14
- 229940082509 xanthan gum Drugs 0.000 claims description 14
- 235000010493 xanthan gum Nutrition 0.000 claims description 14
- 229910001510 metal chloride Inorganic materials 0.000 claims description 13
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 9
- 229940079864 sodium stannate Drugs 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Chemical group 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910018957 MClx Inorganic materials 0.000 claims description 7
- FAAXSAZENACQBT-UHFFFAOYSA-N benzene-1,2,4,5-tetracarbonitrile Chemical compound N#CC1=CC(C#N)=C(C#N)C=C1C#N FAAXSAZENACQBT-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001621 bismuth Chemical class 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000005402 stannate group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- 239000002000 Electrolyte additive Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 230000008719 thickening Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- HLWTXUGKVRYNBH-UHFFFAOYSA-N 1,3,4,6-tetramethylcyclohexa-2,4-diene-1-carbonitrile Chemical compound CC1(C(C=C(C(=C1)C)C)C)C#N HLWTXUGKVRYNBH-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011808 electrode reactant Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses an electrolyte for an aluminum-air battery and a preparation method thereofThe method consists of an alkaline solution, soluble covalent organic framework polymers (COFs), a thickening agent and an inorganic salt. In the invention, the soluble covalent organic framework polymer is added into the electrolyte, the soluble covalent organic framework polymer can form a two-dimensional plane structure due to the connection of the rigid conjugated skeleton of the soluble covalent organic framework polymer, the surface of the soluble covalent organic framework polymer contains abundant nitrogen coordination metal atom centers and abundant pore canal structures, the abundant pore canal structures have stronger solvent absorption and metal adsorption effects, and the metal atom centers and OH‑The solvent molecules can form stronger interaction, so that the COFs can be dissolved in an alkaline solution and form a solution system; in the electrolyte of the alkaline aluminum air battery, the dissolved two-dimensional plane COFs can be adsorbed on the surface of the aluminum negative electrode through strong adsorption capacity, and a covering film is formed to prevent partial free water from evolving hydrogen on the electrode.
Description
Technical Field
The invention belongs to the technical field of air batteries, and particularly relates to an electrolyte for an aluminum air battery and a preparation method of the electrolyte.
Background
The development of new energy automobiles and electronic products is increasing, and the requirement on the energy density of a power supply is higher and higher, so that the traditional lithium ion battery is limited by electrode materials and is difficult to meet urgent requirements. The metal-air battery is a new generation high energy density battery which takes metal as a cathode and oxygen in air as a positive electrode reactant, wherein the aluminum-air battery is widely concerned due to the advantages of high safety, low cost, environmental friendliness, high theoretical specific energy (8100Wh/kg) and the like. The aluminum-air battery electrolyte consists of a neutral aqueous solution or an alkaline aqueous solution, and an aluminum cathode in the neutral electrolyte reacts to form Al +3OH-→Al(OH)3↓+3e-(E0(-1.66V), the generated aluminum hydroxide is flocculent precipitate, and is continuously accumulated along with the discharge product of the battery, so that the aluminum cathode is seriously passivated, the battery voltage is low, and the discharge stability is poor. Therefore, the existing aluminum-air battery mostly adopts a strong base electrolyte system of NaOH or KOH, and the reaction of the negative electrode of the system is Al +4OH-→Al(OH)4 -+3e-(E0-2.34V), the product is readily soluble and the cell open circuit voltage is significantly higher than in the neutral system. However, in a strong alkali system, the aluminum negative electrode is easy to corrode to generate hydrogen, so that the polarization of the battery is increased, the internal resistance is increased, the discharge efficiency is low, the performance is difficult to exert, and the utilization rate of aluminum is low.
Aiming at the problem that an aluminum cathode is easy to corrode and evolve hydrogen in a strong alkaline electrolyte system, the current research mostly adopts aluminum cathode alloying and electrolyte additive adding modes to slow down. The aluminum cathode alloying needs to carry out high-temperature melting treatment on the aluminum and add a plurality of elements for compounding, the energy consumption is high, and the preparation process is complicated. And the additive is directly added into the electrolyte, so that the electrochemical performance of the aluminum air battery is simply and effectively improved.
The single inorganic or organic additive can inhibit hydrogen evolution corrosion to a certain extent, but most of the inorganic additives are film-forming inorganic additives, although the inorganic additives can act to a certain extent, deposited film layers obtained on the surfaces of the electrodes are not compact, loose and porous, and are easy to fall off, so that the inhibition effect is poor; although the organic additive has the function of tightly covering the surface of the electrode, the addition amount is increased, so that the activity of the electrode is easily reduced, the passivation is increased, and the electrochemical performance of the battery is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an electrolyte for an aluminum air battery and a preparation method thereof, wherein the electrolyte has a composition which can effectively inhibit hydrogen evolution corrosion so as to improve the electrochemical performance of the battery.
The electrolyte for the aluminum-air battery consists of an alkaline solution, soluble covalent organic framework polymers (COFs), a thickening agent and inorganic salt; the concentration of the soluble covalent organic framework polymer in an alkaline solution is 0.05-5 g/L, the mass concentration of the thickening agent in the electrolyte is 0.1-5 wt%, two inorganic salts A and B are required to be added into the inorganic salt, the concentration of the inorganic salt in the alkaline solution is 0.1-20 g/L, and the inorganic salt B accounts for 0-40 wt% of the total amount of the inorganic salt.
The preparation method of the soluble covalent organic framework polymers (COFs) comprises the following steps:
(1) taking metal chloride MClxAnd 1,2,4, 5-benzene tetracyanonitrile monomer and dissolved in ethylene glycol to obtain a mixed system;
(2) and (2) adding a catalyst into the mixed system in the step (1), uniformly mixing, placing in a microwave reactor for reaction, and after the reaction is finished, cooling, filtering, washing and drying the reaction solution to obtain the soluble covalent organic framework polymer.
In the step (1), the metal chloride MClxIs one or more of ferric chloride, cobalt chloride, manganese chloride, nickel chloride and zinc chloride, preferably, zinc chloride or nickel chloride; metal chloride MClxThe mass ratio of the 1,2,4, 5-benzene tetracarbonitrile to the 1,2,4, 5-benzene tetracarbonitrile is (1-2) to (1-4); the ratio of the mass of the glycol to the total mass of the metal chloride and the 1,2,4, 5-benzenetetracarbonitrile is (10-15): 1.
In the step (2), the catalyst is one of triethylene diamine (TEDA) or 1, 8-diazabicycloundece-7-ene (DBU), the ratio of the mass of the catalyst to the total mass of the metal chloride and the polymer monomer is 1 (5-20), preferably, the catalyst is 1, 8-diazabicycloundece-7-ene (DBU), and the ratio of the catalyst to the metal chloride and the 1,2,4, 5-benzene tetracyanonitrile is 1 (10-20); the reaction temperature is 80-240 ℃, and the reaction time is 10-30 min.
The metal atom center of the soluble covalent organic framework polymer is one or more of iron, cobalt, manganese, nickel and zinc.
The alkaline solution is sodium hydroxide or potassium hydroxide solution, the concentration is 2-8 mol/L, and the preferable concentration is 4-6 mol/L; the thickener is one or more of xanthan gum, carboxymethyl cellulose, polyoxyethylene and polyurethane, preferably, the molecular weight of xanthan gum in the thickener is (4-4.5) x 106The molecular weight of the carboxymethyl cellulose is (7-9) multiplied by 105Polyoxyethylene having a molecular weight of 5 to 8 x 105The molecular weight of the polyurethane is (1.8-3) x 105Further preferably, the thickener is xanthan gum or polyurethane; the inorganic salt A is one or more of stannate, zinc salt, bismuth salt and oxides of zinc and bismuth; the inorganic salt B is one or more of tungstate, molybdate, cerium salt, calcium salt and oxides of cerium and calcium; preferably, the inorganic salt A is sodium stannate or zinc oxide; the inorganic salt B is sodium tungstate, cerium nitrate or calcium oxide.
The preparation method of the electrolyte for the aluminum-air battery comprises the following steps:
preparing an alkaline solution, adding inorganic salts A and B, adding a thickening agent after fully dissolving, stirring for a set time at a set speed to obtain a thickened electrolyte system, standing, heating, adding a covalent organic framework polymer, stirring uniformly, and naturally cooling to obtain an electrolyte.
The set speed is 800-1500 r/min, and the set time is 5-15 min; standing for 10-20 min, and heating at 50-80 ℃.
In the preparation method, the adding sequence and the process of various raw materials are very critical, the adding sequence of the raw materials is very important for forming the high-performance electrolyte, and the parameters in the preparation step are controlled appropriately. The inorganic salt is preferably added before the thickener because it dissolves well and quickly in water. The covalent organic framework polymer is slowly dissolved, so that the covalent organic framework polymer is not easily dispersed in an aqueous solution without a thickening agent and partially aggregated and subsided, and the covalent organic framework polymer is added after a thickening system is formed, thereby being beneficial to good dispersion and stability of the covalent organic framework polymer in the system. The thickening agent is added and then stirred at a specific speed, if the stirring speed is too low, a thickening system can agglomerate and is not easy to achieve uniformity, and if the stirring speed is too high and the shearing force is too large, the molecular group can be reduced, and the thickening effect is poor. The purpose of standing is to allow air bubbles in the thickened system to escape and stabilize the system.
The invention has the beneficial effects that:
in the invention, soluble covalent organic framework polymer is added into electrolyteThe soluble covalent organic framework polymer can form a two-dimensional plane structure due to the connection of the rigid conjugated frameworks of the soluble covalent organic framework polymer, and the surface of the soluble covalent organic framework polymer contains abundant nitrogen coordination metal atom centers and abundant pore channel structures. Rich pore canal structure has strong solvent absorption and metal adsorption effects, and metal atom center and OH-Etc. can form strong interaction, so that the COFs can be dissolved in an alkaline solution and form a solution system. In the electrolyte of the alkaline aluminum air battery, the dissolved two-dimensional plane COFs can be adsorbed on the surface of an aluminum cathode through strong adsorption capacity to form a covering film to prevent partial free water from hydrogen evolution on the electrode, but the single use effect is poor; the added stannic acid radical, zinc salt, bismuth salt and oxides thereof are reduced at the electrode interface to form simple substance metal, which plays the roles of activating the electrode and improving hydrogen evolution overpotential; tungstate, molybdate, cerium salt, calcium salt and oxides thereof generate precipitates in alkaline electrolyte and deposit on the interface of the aluminum electrode, so that the effect of forming a film on the surface to inhibit the corrosion hydrogen evolution reaction is achieved; however, when the additive is used alone, a product film layer formed is not compact, loose and porous, is easy to fall off and has poor stability. Through the cooperative COFs, the product layer is tightly connected with the surface of the aluminum cathode by utilizing the adsorption capacity of the COFs, and in addition, a covering film formed by the COFs by self adsorption has a certain hydrogen evolution inhibiting effect; the addition of the thickening agent enables COFs to be dispersed more uniformly in an electrolyte system without precipitation, and meanwhile, the solution system can be stabilized, so that the surface tension is reduced, and the problems of self-discharge and equipment corrosion of a large number of batteries caused by alkaline solution alkali climbing are solved.
Therefore, the soluble covalent organic framework polymer, the thickening agent and the inorganic composite additive are comprehensively used, the aluminum cathode can be activated while a stable covering film is formed on the surface of the aluminum cathode, the corrosion hydrogen evolution of the aluminum cathode is inhibited, the utilization rate of aluminum is improved, the open-circuit potential and the discharge stability of the aluminum cathode are also improved, and in addition, the problems of a large amount of self-discharge of a battery and equipment corrosion caused by alkali climbing of an alkaline solution are solved.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
Preparation of electrolyte additives COFs: taking ZnCl2And 5g of monomer 1,2,4, 5-tetramethylbenzonitrile respectively are dissolved in 100g of ethylene glycol, 0.8g of 1, 8-diazabicycloundecen-7-ene is added and mixed uniformly, the reaction kettle is placed in a microwave reactor and heated to 180 ℃ for reaction for 15min, and then the reaction kettle is cooled, filtered, washed and dried to obtain the target product covalent organic framework polymer (Zn-COFs) as an electrolyte additive.
Preparing an electrolyte for the aluminum air battery: firstly, 500mL of 4mol/L NaOH solution is prepared, then 4g/L sodium stannate and 1g/L calcium oxide are added for dissolution, and then the molecular weight is 4.5 multiplied by 106Stirring 6g of xanthan gum serving as a thickening agent at the speed of 1200r/min for 10min to form a thickening system, standing for 15min, heating to 50 ℃, adding a covalent organic framework polymer (Zn-COFs) in an amount of 0.5g/L, stirring uniformly, naturally cooling to obtain an electrolyte, and applying the electrolyte to an aluminum air battery.
Comparative example 1
Compared to example 1, no covalent organic framework polymer was added;
comparative example 2
Compared with the example 1, sodium stannate and calcium oxide are not added;
comparative example 3
Compared with example 1, no thickener xanthan gum was added;
comparative example 4
Compared to example 1, no covalent organic framework polymer, sodium stannate, calcium oxide and thickener xanthan gum were added.
The results of the corrosion rate and the open circuit potential of the electrolyte applied to the aluminum-air battery in the example 1 and the comparative examples 1 to 4 are shown in table 1, the corrosion of the aluminum cathode is reduced by adding the composite additive in the example 1, and the corrosion rate is 1.8 mg/(cm)2H) and the open circuit potential is-1.58V. In comparative examples 1 to 3, the corrosion cannot be effectively inhibited due to the addition of a small amount of additive components, the corrosion rate of the aluminum cathode is increased, and the open-circuit potential is shifted forward; while the comparative example 4 does not contain any additive component, the corrosion rate is as high as 24.5 mg/(cm)2H), the open circuit potential is positively shifted to-1.30V.
TABLE 1 electrolyte Performance data sheet
Example 2
The preparation of electrolyte additives COFs was the same as in example 1;
preparing an electrolyte for the aluminum air battery: 500ml of 4mol/L NaOH solution is prepared firstly, then 0.8g/L zinc oxide and 0.3g/L cerium nitrate are added for dissolution, and then the molecular weight of 4.5 multiplied by 10 is added6Stirring 6g of xanthan gum serving as a thickening agent at the speed of 1200r/min for 10min to form a thickening system, standing for 15min, heating to 50 ℃, adding a covalent organic framework polymer (Zn-COFs) in an amount of 0.5g/L, stirring uniformly, naturally cooling to obtain an electrolyte, and applying the electrolyte to an aluminum air battery.
Example 3
The preparation of electrolyte additives COFs was the same as in example 1;
preparing an electrolyte for the aluminum air battery: firstly, 500mL of 4mol/L NaOH solution is prepared, then 4g/L sodium stannate and 1g/L calcium oxide are added for dissolution, and then the molecular weight is 2 multiplied by 105Stirring 10g of thickener polyurethane at the speed of 1500r/min for 5min to form a thickening system, standing for 15min, heating to 50 ℃, adding covalent organic framework polymers (Zn-COFs) in an amount of 0.5g/L, stirring uniformly, naturally cooling to obtain electrolyte, and applying the electrolyte to an aluminum air battery.
Example 4
The preparation of electrolyte additives COFs was the same as in example 1;
preparing an electrolyte for the aluminum air battery: firstly, 500mL of 4mol/L NaOH solution is prepared, then 4g/L sodium stannate and 1g/L calcium oxide are added for dissolution, and then the molecular weight is 4.5 multiplied by 106Stirring 6g of xanthan gum serving as a thickening agent at the speed of 1200r/min for 10min to form a thickening system, standing for 15min, heating to 50 ℃, adding a covalent organic framework polymer (Zn-COFs) in an amount of 2g/L, stirring uniformly, naturally cooling to obtain an electrolyte, andthe method is applied to the aluminum air battery.
Example 5
The preparation of electrolyte additives COFs was the same as in example 1;
preparing an electrolyte for the aluminum air battery: firstly, 500mL of 6mol/L NaOH solution is prepared, then 4g/L sodium stannate is added, and then 4.5X 10 molecular weight is added6Stirring 6g of xanthan gum serving as a thickening agent at the speed of 1200r/min for 10min to form a thickening system, standing for 15min, heating to 50 ℃, adding a covalent organic framework polymer (Zn-COFs) in an amount of 2g/L, stirring uniformly, naturally cooling to obtain an electrolyte, and applying the electrolyte to an aluminum air battery.
The results of the corrosion rate and open circuit potential of the electrolytes of examples 2 to 5 applied to an aluminum-air battery are shown in Table 2, and compared to example 1, in example 2, when 0.8g/L zinc oxide and 0.3g/L cerium nitrate were used instead of 4g/L sodium stannate and 1g/L calcium oxide, the corrosion inhibition effect was only slightly lower than that of example 1, and the corrosion rate was 3.2 mg/(cm) of cerium nitrate2H), the open circuit potential reaches-1.52V; example 3 compared with example 1, the thickener has 10g of polyurethane instead of 6g of xanthan gum, and the corrosion inhibition effect is equivalent to that of example 1 and is 2.9 mg/(cm)2H); example 4 compared with example 1, when the amount of the covalent organic framework polymer is increased from 0.5g/L to 2g/L, excessive COFs can easily fall off to cause poor corrosion inhibition effect; example 5 compared with example 4, the concentration of the sodium hydroxide solution is increased, and the corrosion is slightly increased due to the addition of less B-type inorganic salt; the corrosion inhibition effect of the electrolytes in examples 2-5 is still better than that of comparative examples 1-4 with or without additive components.
TABLE 2 tables of Performance data of electrolytes in examples 2 to 5
Example 6
Preparation of electrolyte additives COFs: taking NiCl25g of 1,2,4, 5-benzenetetracarboxylic acid nitrile, 8g each, were placed in a reaction vessel, and dissolved in 150g of ethylene glycol, to which triethylene glycol was added0.9g of amine (TEDA) is mixed uniformly, the reaction kettle is placed in a microwave reactor and heated to 200 ℃ for reaction for 10min, and then the reaction kettle is cooled, filtered, washed and dried to obtain a target product, namely covalent organic framework polymers (Ni-COFs), which serve as electrolyte additives.
Preparing an electrolyte for the aluminum air battery: firstly, 500mL of 6mol/L KOH solution is prepared, then 4g/L sodium nitrate and 1g/L sodium molybdate are added for dissolution, and then the molecular weight is 4.5 multiplied by 106Stirring 8g of xanthan gum serving as a thickening agent at the speed of 1200r/min for 15min to form a thickening system, standing for 20min, heating to 70 ℃, adding a covalent organic framework polymer (Ni-COFs) in an amount of 0.7g/L, stirring uniformly, naturally cooling to obtain an electrolyte, and applying the electrolyte to an aluminum air battery
Example 7
Preparation of electrolyte additives COFs: taking CoCl25g and 8g of monomer 1,2,4, 5-benzene tetranitrile are respectively dissolved in a reaction kettle, 150g of ethylene glycol is added with 0.9g of triethylene diamine (TEDA) and uniformly mixed, the reaction kettle is placed in a microwave reactor and heated to 200 ℃ for reaction for 10min, and then the reaction kettle is cooled, filtered, washed and dried to obtain the target product, namely the covalent organic framework polymer (Co-COFs), which is used as an electrolyte additive.
Preparing an electrolyte for the aluminum air battery: firstly, 500mL of 6mol/L KOH solution is prepared, then 4g/L sodium nitrate and 1g/L sodium molybdate are added for dissolution, and then the molecular weight is 8 multiplied by 10510g of thickener carboxymethyl cellulose, stirring at the speed of 1200r/min for 15min to form a thickening system, standing for 20min, heating to 60 ℃, adding covalent organic framework polymers (Co-COFs) in an amount of 1.0g/L, stirring uniformly, naturally cooling to obtain electrolyte, and applying the electrolyte to an aluminum air battery.
TABLE 3 tables of Performance data of electrolytes in examples 6 to 7
Claims (8)
1. An electrolyte for an aluminum air battery is characterized by comprising an alkaline solution, soluble covalent organic framework polymers (COFs), a thickening agent and inorganic salt; the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration is 2-8 mol/L; the concentration of the soluble covalent organic framework polymer in an alkaline solution is 0.05-5 g/L; the thickening agent is one or more of xanthan gum, carboxymethyl cellulose, polyoxyethylene and polyurethane, and the mass concentration of the thickening agent in the electrolyte is 0.1-5 wt%; the inorganic salt needs to be added with two types of inorganic salt A and inorganic salt B, wherein the inorganic salt A is one or more of stannate, zinc salt, bismuth salt and oxides of zinc and bismuth, and the inorganic salt B is one or more of tungstate, molybdate, cerium salt, calcium salt and oxides of cerium and calcium; the concentration of the inorganic salt in the alkaline solution is 0.1-20 g/L, and the inorganic salt B accounts for 0-40 wt% of the total amount of the inorganic salt.
2. The electrolyte for aluminum-air batteries according to claim 1, wherein the method for preparing the soluble covalent organic framework polymers (COFs) comprises the following steps:
(1) taking metal chloride MClxAnd 1,2,4, 5-benzene tetracyanonitrile monomer and dissolved in ethylene glycol to obtain a mixed system;
(2) and (2) adding a catalyst into the mixed system in the step (1), uniformly mixing, placing in a microwave reactor for reaction, and after the reaction is finished, cooling, filtering, washing and drying the reaction solution to obtain the soluble covalent organic framework polymer.
3. The electrolyte for aluminum-air battery as recited in claim 2, wherein in the step (1), the metal chloride MClxIs one or more of ferric chloride, cobalt chloride, manganese chloride, nickel chloride and zinc chloride, metal chloride MClxThe mass ratio of the 1,2,4, 5-benzene tetracarbonitrile to the 1,2,4, 5-benzene tetracarbonitrile is (1-2) to (1-4); the ratio of the mass of the glycol to the total mass of the metal chloride and the 1,2,4, 5-benzenetetracarbonitrile is (10-15): 1; in the step (2), the catalyst is one of triethylene diamine or 1, 8-diazabicycloundec-7-ene, and the mass of the catalyst is equal to the sum of the metal chloride and the polymer monomerThe mass ratio is 1 (5-20), the reaction temperature is 80-240 ℃, and the reaction time is 10-30 min.
4. The electrolyte for an aluminum-air battery according to claim 3, wherein in the step (1), the metal chloride MClxIs zinc chloride or nickel chloride; in the step (2), the catalyst is 1, 8-diazabicycloundecen-7-ene, and the ratio of the catalyst to the total mass of the metal chloride and the 1,2,4, 5-benzenetetracarboxylic nitrile is 1 (10-20).
5. The electrolyte for an aluminum-air battery as recited in claim 1, wherein the alkaline solution
The concentration is 4-6 mol/L; the molecular weight of the xanthan gum in the thickening agent is (4-4.5) multiplied by 106The molecular weight of the carboxymethyl cellulose is (7-9) multiplied by 105Polyoxyethylene having a molecular weight of 5 to 8 x 105The molecular weight of the polyurethane is (1.8-3) x 105(ii) a The inorganic salt A is sodium stannate or zinc oxide; the inorganic salt B is sodium tungstate, cerium nitrate or calcium oxide.
6. The electrolyte for an aluminum-air battery according to claim 5, wherein the thickener is xanthan gum or polyurethane.
7. The method for producing an electrolyte solution for an aluminum-air battery according to any one of claims 1 to 6, comprising the steps of:
preparing an alkaline solution, adding inorganic salts A and B, adding a thickening agent after fully dissolving, stirring for a set time at a set speed to obtain a thickened electrolyte system, standing, heating, adding a covalent organic framework polymer, stirring uniformly, and naturally cooling to obtain an electrolyte.
8. The method for producing an electrolyte for an aluminum-air battery according to claim 7, wherein the set speed is 800 to 1500r/min and the set time is 5 to 15 min; standing for 10-20 min, and heating at 50-80 ℃.
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